Organocatalytic Dearomatization of β‐Naphthols through a 1,6‐Conjugated Addition of Alkynyl 7‐Methylene‐7H‐indoles Formed In Situ DOI

Sheng-Jie Kang,

Xiaohong Liu, Yi Zhang

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 15, 2024

Abstract Organocatalytic dearomatization of β‐naphthols has been achieved via a 1,6‐conjugated addition 2‐naphthols to alkynyl 7‐methylene‐7 H ‐indoles in situ generated from α‐(7‐indolyl)methanols. In the presence racemic phosphoric acid, series tetrasubstituted allenes was obtained high yields. Particularly, with aid chiral asymmetric investigated, affording axially moderate enantioselectivity.

Language: Английский

Organocatalytic Enantioselective 1,8-Addition for the Synthesis of Chiral Tetraarylmethanes from 2-Naphthol/Naphthalen-2-amine-Based Tertiary Alcohols DOI

Meiwen Liu,

Boming Shen,

Chang Liu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(26), P. 14562 - 14569

Published: June 21, 2023

Catalytic enantioselective construction of optically active tetraarylmethanes remains a challenging issue in the field asymmetric synthesis because overwhelming steric hindrance and formidable stereocontrol that existed all-aryl-substituted quaternary carbon stereocenter. Here, we reported an organocatalytic chiral from racemic tertiary alcohols. With aid phosphoric acid catalyst, 6-methylenenaphthalen-2(6H)-ones were generated situ 6-(hydroxydiarylmethyl)naphthalen-2-ols, followed by stereoselective 1,8-conjugate addition to afford corresponding high excellent yields with enantioselectivities. Furthermore, scope alcohols has been successfully enlarged 6-(hydroxydiphenylmethyl)naphthalen-2-amines. Notably, it is first time use 2-naphthol/naphthalen-2-amine unit as auxiliary group generate α,β,γ,δ,ε,ζ-conjugate systems, which have involved remote stereocontrolled reactions. Particularly, stereoconvergent formal nucleophilic substitution reaction triarylmethanols achieved for tetraarylmethanes. In addition, DFT calculations applied provide guidance design additional understand origin stereoselectivity.

Language: Английский

Citations

19
Organocatalytic enantioselective reaction of tertiary α-(7-indolyl)methanols with tryptamines DOI

Zhibin Yue,

Boming Shen,

Jie Cao

et al.

Organic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(14), P. 3662 - 3668

Published: Jan. 1, 2023

With the aid of chiral phosphoric acid, enantioselective 1,6-addition tryptamines to in situ formed alkynyl 7-methylene-7 H -indoles from tertiary α-(7-indolyl)methanols has been established, furnishing axially tetrasubstituted allenes high yields.

Language: Английский

Citations

16
Organocatalytic Enantioselective 1,12‐Addition of Alkynyl Biphenyl Quinone Methides Formed In Situ DOI
Xing Wang,

Boming Shen,

Meiwen Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: May 3, 2024

The chemistry of quinone methides formed in situ has been flourishing recent years. In sharp contrast, the development and utilization biphenyl are rare. this study, we achieved a remote stereocontrolled 1,12-conjugate addition for first time. presence suitable chiral phosphoric acid, alkynyl were generated from α-[4-(4-hydroxyphenyl)phenyl]propargyl alcohols, followed by enantioselective with indole-2-carboxylates. strategy enabled alcohols to serve as efficient allenylation reagents, providing practical access broad range axially allenes bearing (1,1'-biphenyl)-4-ol unit, which previously less accessible. Combined control experiments, density functional theory calculations shed light on reaction mechanism, indicating that enantioselectivity originates nucleophilic methides. Notably, not only versatile intermediates was confirmed but also organocatalytic 1,12-addition established.

Language: Английский

Citations

5
Organocatalytic Remote Stereocontrolled Synthesis of Tetrasubstituted Allenes via Asymmetric 1,8‐Addition of Propargylic Aza‐p‐Quinone Methides DOI

Zhibin Yue,

Yan Xia,

Boming Shen

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(5), P. 1078 - 1083

Published: Jan. 17, 2024

Abstract An organocatalytic remote stereocontrolled 1,8‐conjugated addition of in situ formed propargylic aza‐ p ‐QMs from α‐(4‐aminophenyl) alcohols and indole‐2‐carboxylates was developed, affording axially chiral tetrasubstituted allenes 62–99% yield with 52–99% ee. The synthetic strategy not only enriches the chemistry ‐quinone methides, but also provides an alternative tool for preparation allenes.

Language: Английский

Citations

4
Organocatalytic Remote Stereocontrolled Additions of In Situ Formed Electron‐Deficient Conjugate Systems DOI

Zhibin Yue,

Fang Fang, Yan Xia

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(12), P. 1926 - 1933

Published: May 17, 2023

Abstract Conjugate addition is one of the most powerful and practical methods for formation carbon‐carbon carbon‐heteroatom bonds in organic synthesis. Owing to rapid development asymmetric catalysis, significant progress has been made field conjugate addition, such as 1,4‐addition 1,6‐addition. However, formidable challenge controlling chemo‐, regio‐ stereoselectivity arises with extended conjugated systems. Recently, aid Brønsted acids functionalized benzyl alcohols indolylmethanols successfully developed suitable precursors electron‐deficient systems organocatalytic remote stereocontrolled additions. This review investigates advances enantioselective 1,8‐conjugate 1,10‐conjugate situ formed from alcohols, which organized according substrates.

Language: Английский

Citations

9
Organocatalytic Enantioselective 1,12‐Addition of Alkynyl Biphenyl Quinone Methides Formed In Situ DOI
Xing Wang,

Boming Shen,

Meiwen Liu

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(29)

Published: May 3, 2024

Abstract The chemistry of quinone methides formed in situ has been flourishing recent years. In sharp contrast, the development and utilization biphenyl are rare. this study, we achieved a remote stereocontrolled 1,12‐conjugate addition for first time. presence suitable chiral phosphoric acid, alkynyl were generated from α‐[4‐(4‐hydroxyphenyl)phenyl]propargyl alcohols, followed by enantioselective with indole‐2‐carboxylates. strategy enabled alcohols to serve as efficient allenylation reagents, providing practical access broad range axially allenes bearing (1,1′‐biphenyl)‐4‐ol unit, which previously less accessible. Combined control experiments, density functional theory calculations shed light on reaction mechanism, indicating that enantioselectivity originates nucleophilic methides. Notably, not only versatile intermediates was confirmed but also organocatalytic 1,12‐addition established.

Language: Английский

Citations

2
Beyond 1,4-addition of in-situ generated (aza-)quinone methides and indole imine methides DOI

Yanli Li,

Zhiming Li, Kai‐Kai Wang

et al.

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 35(7), P. 109322 - 109322

Published: Nov. 19, 2023

Language: Английский

Citations

4
Organocatalytic Dearomatization of β‐Naphthols through a 1,6‐Conjugated Addition of Alkynyl 7‐Methylene‐7H‐indoles Formed In Situ DOI

Sheng-Jie Kang,

Xiaohong Liu, Yi Zhang

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 15, 2024

Abstract Organocatalytic dearomatization of β‐naphthols has been achieved via a 1,6‐conjugated addition 2‐naphthols to alkynyl 7‐methylene‐7 H ‐indoles in situ generated from α‐(7‐indolyl)methanols. In the presence racemic phosphoric acid, series tetrasubstituted allenes was obtained high yields. Particularly, with aid chiral asymmetric investigated, affording axially moderate enantioselectivity.

Language: Английский

Citations

0